Alkylaromatic production process

ABSTRACT

The present disclosure provides a process for selectively producing a desired monoalkylated aromatic compound comprising the step of contacting in a reaction zone an alkylatable aromatic compound with an alkylating agent in the presence of catalyst comprising a porous crystalline material under at least partial liquid phase conditions, said catalyst manufactured from extrudate to comprise catalytic particulate material of from about 125 microns to about 790 microns in size, having an Effectiveness Factor increased from about 25% to about 750% from that of the original extrudate, and having an external surface area to volume ratio of greater than about 79 cm −1 .

PRIORITY CLAIM

This application is a continuation of U.S. application Ser. No.12/019,955, filed Jan. 25, 2008, now U.S. Pat. No. 7,816,574, whichclaims the benefit of U.S. Provisional Application No. 60/900,638, filedFeb. 9, 2007, the entirety of which is incorporated by reference.

BACKGROUND OF THE INVENTION

The present disclosure relates to a process mechanism for producingalkylaromatics, especially monoalkylaromatic compounds, for exampleethylbenzene, cumene and sec-butylbenzene.

The alkylaromatic compounds ethylbenzene and cumene, for example, arevaluable commodity chemicals which are used industrially for theproduction of styrene monomer and coproduction of phenol and acetonerespectively. In fact, a common route for the production of phenolcomprises a process which involves alkylation of benzene with propyleneto produce cumene, followed by oxidation of the cumene to thecorresponding hydroperoxide, and then cleavage of the hydroperoxide toproduce equal molar amounts of phenol and acetone. Ethylbenzene may beproduced by a number of different chemical processes. One process whichhas achieved a significant degree of commercial success is the vaporphase alkylation of benzene with ethylene in the presence of a solid,acidic ZSM-5 zeolite catalyst. Examples of such ethylbenzene productionprocesses are described in U.S. Pat. No. 3,751,504 (Keown), U.S. Pat.No. 4,547,605 (Kresge) and U.S. Pat. No. 4,016,218 (Haag).

Another process which has achieved significant commercial success is theliquid phase process for producing ethylbenzene from benzene andethylene since it operates at a lower temperature than the vapor phasecounterpart and hence tends to result in lower yields of by-products.For example, U.S. Pat. No. 4,891,458 (Innes) describes the liquid phasesynthesis of ethylbenzene with zeolite Beta, whereas U.S. Pat. No.5,334,795 (Chu) describes the use of MCM-22 in the liquid phasesynthesis of ethylbenzene.

Cumene has for many years been produced commercially by the liquid phasealkylation of benzene with propylene over a Friedel-Crafts catalyst,particularly solid phosphoric acid or aluminum chloride. More recently,however, zeolite-based catalyst systems have been found to be moreactive and selective for propylation of benzene to cumene. For example,U.S. Pat. No. 4,992,606 (Kushnerick) describes the use of MCM-22 in theliquid phase alkylation of benzene with propylene.

Typically, the zeolite catalysts employed in hydrocarbon conversionprocesses, such as aromatics alkylation, are in the form of cylindricalextrudates. However, it is known from, for example, U.S. Pat. No.3,966,644 (Gustafson) that shaped catalyst particles having a highsurface to volume ratio, such as those having a polylobal cross-section,can produce improved results in processes which are diffusion limited,such as the hydrogenation of reside.

Moreover, it is known from U.S. Pat. No. 4,441,990 (Huang) that apolylobal catalyst particle having a non-cylindrical centrally locatedaperture can reduce the diffusion path for reagents and the pressuredrop across packed catalyst beds while minimizing catalyst loss due tobreakage, abrasion and crushing. In particular, Example 8 of the '990patent discloses that hollow trilobal and quadrulobal ZSM-5 catalystsare more active and selective for the ethylation of benzene at 410° C.and 2169 kPa-a (kilopascal absolute) pressure than solid cylindricalcatalysts of the same length. Under these conditions, the reagents arenecessarily in the vapor phase.

Current commercial catalysts used most often for these processmechanisms are 0.159 cm cylindrical or 0.127 cm quadrulobal extrudates.The prior extrudates are roughly 1550 to 1600 microns in size, and thelatter are roughly 1250 to 1300 microns in size.

Existing alkylation processes for producing alkylaromatic compounds, forexample ethylbenzene and cumene, inherently produce polyalkylatedspecies as well as the desired monoalkylated product. It is thereforenormal to transalkylate the polyalkylated species with additionalaromatic feed, for example benzene, to produce additional monoalkylatedproduct, for example ethylbenzene or cumene, either by recycling thepolyalkylated species to the alkylation reactor or, more frequently, byfeeding the polyalkylated species to a separate transalkylation reactor.Examples of catalysts which have been used in the alkylation of aromaticspecies, such as alkylation of benzene with ethylene or propylene, andin the transalkylation of polyalkylated species, such aspolyethylbenzenes and polyisopropylbenzenes, are listed in U.S. Pat. No.5,557,024 (Cheng) and include MCM-49, MCM-22, PSH-3, SSZ-25, zeolite X,zeolite Y, zeolite Beta, acid dealuminized mordenite and TEA-mordenite.Transalkylation over a small crystal (<0.5 micron) form of TEA-mordeniteis also disclosed in U.S. Pat. No. 6,984,764 (Roth et al).

Where the alkylation step is performed in the liquid phase, it is alsodesirable to conduct the transalkylation step under liquid phaseconditions. However, by operating at relatively low temperatures, liquidphase processes impose increased requirements on the catalyst,particularly in the transalkylation step where the bulky polyalkylatedspecies must be converted to additional monoalkylated product withoutproducing unwanted by-products. This has proven to be a significantproblem in the case of cumene production where existing catalysts haveeither lacked the desired activity or have resulted in the production ofsignificant quantities of by-products such as ethylbenzene andn-propylbenzene.

U.S. Pat. No. 6,888,037 (Dandekar et al) discloses a process forproducing cumene which comprises the step of contacting benzene andpropylene under at least partial liquid phase alkylating conditions witha particulate molecular sieve alkylation catalyst, wherein the particlesof said alkylation catalyst have a surface area to volume ratio of about80 to less than 200 inch⁻¹. According to U.S. Pat. No. 6,888,037, theliquid phase propylation of benzene, unlike the liquid phase ethylationof benzene, is sensitive to intraparticle (macroporous) diffusionlimitations. In particular, by selecting the shape and size of theparticles of the alkylation catalyst such that the surface to volumeratio is within the specified range, the intraparticle diffusiondistance can be decreased without excessively increasing the pressuredrop across the first catalyst bed. As a result, the activity of thecatalyst for the propylation of benzene can be increased, while at thesame time the selectivity of the catalyst towards undesirablepolyalkylated species, such as diisopropylbenzene (DIPB) can be reduced.

U.S. Patent Application Ser. No. 60/808,192, published as PCTPublication No. WO2007/139629, discloses a process for producing amonoalkylated aromatic compound in an alkylation reaction zone, saidprocess comprising the steps of (1) providing said alkylation reactionzone with an alkylatable aromatic compound, an alkylating agent, and acatalytic particulate material; and (2) contacting said alkylatablearomatic compound and said alkylating agent with said catalyticparticulate material in said alkylation reaction zone maintained underalkylation conditions, to form a product comprised of said monoalkylatedaromatic compound and polyalkylated aromatic compound(s), wherein themajority of said catalytic particulate material has a surface area tovolume ratio of greater than about 79 cm⁻¹.

According to the present disclosure, it has now unexpectedly been foundthat the reaction of the present disclosure conducted in the presence ofa specific catalyst manufactured from extrudate to comprise catalyticparticulate material within the narrow range of from about 125 micronsto about 790 microns in size and having an Effectiveness Factor,hereafter defined, increased from about 25% to about 750% from that ofthe original extrudate, yields a unique combination of activity andselectivity while not subjecting the process to unacceptable pressuredrop across the catalyst bed. This is especially the case when theprocess involves liquid phase alkylation for manufacture ofmonoalkylated product, particularly for the liquid phase alkylation ofbenzene to ethylbenzene or cumene. This obviates the demand in manyinstances for the difficult transalkylation reaction for conversion ofunwanted bulky polyalkylated species in such a process.

SUMMARY OF THE INVENTION

According to the present disclosure, there is provided an improvedprocess for selectively producing a desired monoalkylated aromaticcompound comprising the step of contacting in a reaction zone analkylatable aromatic compound with an alkylating agent in the presenceof catalyst comprising a porous crystalline material under at leastpartial liquid phase conditions, the catalyst manufactured fromextrudate to comprise catalytic particulate material of from about 125microns to about 790 microns in size and having an Effectiveness Factor,hereafter defined, increased from about 25% to about 750% from that ofthe original extrudate. An aspect of the present disclosure is animproved alkylation process for the selective production of monoalkylbenzene in a reaction zone comprising the step of reacting benzene withan alkylating agent under alkylation conditions sufficient to causealkylation in the presence of alkylation catalyst comprising a porouscrystalline material, the catalyst manufactured from extrudate tocomprise catalytic particulate material of from about 125 microns toabout 790 microns in size and having an Effectiveness Factor, hereafterdefined, increased from about 25% to about 750% from that of theoriginal extrudate. The catalyst for use in the present process maycomprise, for example, a MCM-22 family material, a crystalline molecularsieve having the structure of zeolite Beta, or one having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms, the catalyst manufactured fromextrudate to comprise catalytic particulate material of from about 125microns to about 790 microns in size and having an Effectiveness Factor,hereafter defined, increased from about 25% to about 750% from that ofthe original extrudate. More particularly, the catalyst for use hereinmay comprise a crystalline molecular sieve having the structure of Beta,a MCM-22 family material, e.g. MCM-22, or a mixture thereof.

The catalyst for use in the present disclosure preferably comprises aMCM-22 family material, such as for example a crystalline silicatehaving the structure of MCM-22, PSH-3, SSZ-25, ERB-1, ITQ-1, ITQ-2,ITQ-30, MCM-36, MCM-49, MCM-56 and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

All patents, patent applications, test procedures, priority documents,articles, publications, manuals, and other documents cited herein arefully incorporated by reference to the extent such disclosure is notinconsistent with the present disclosure and for all jurisdictions inwhich such incorporation is permitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

As used in this specification, the term “framework type” is used in thesense described in the “Atlas of Zeolite Framework Types,” 2001.

As used herein, the numbering scheme for the Periodic Table Groups isused as in Chemical and Engineering News, 63(5), 27 (1985).

The term “MCM-22 family material” (or “material of the MCM-22 family” or“molecular sieve of the MCM-22 family”), as used herein, includes:molecular sieves made from a common first degree crystalline buildingblock “unit cell having the MWW framework topology”. A unit cell is aspatial arrangement of atoms which is tiled in three-dimensional spaceto describe the crystal as described in the “Atlas of Zeolite FrameworkTypes”, Fifth edition, 2001, the entire content of which is incorporatedas reference; molecular sieves made from a common second degree buildingblock, a 2-dimensional tiling of such MWW framework type unit cells,forming a “monolayer of one unit cell thickness”, preferably one c-unitcell thickness; molecular sieves made from common second degree buildingblocks, “layers of one or more than one unit cell thickness”, whereinthe layer of more than one unit cell thickness is made from stacking,packing, or binding at least two monolayers of one unit cell thick ofunit cells having the MWW framework topology. The stacking of suchsecond degree building blocks can be in a regular fashion, an irregularfashion, a random fashion, and any combination thereof; or molecularsieves made by any regular or random 2-dimensional or 3-dimensionalcombination of unit cells having the MWW framework topology.

The MCM-22 family materials are characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 3.57±0.07and 3.42±0.07 Angstroms (either calcined or as-synthesized). The MCM-22family materials may also be characterized by having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms (either calcined or as-synthesized).The X-ray diffraction data used to characterize the molecular sieve areobtained by standard techniques using the K-alpha doublet of copper asthe incident radiation and a diffractometer equipped with ascintillation counter and associated computer as the collection system.Materials belong to the MCM-22 family include MCM-22 (described in U.S.Pat. No. 4,954,325), PSH-3 (described in U.S. Pat. No. 4,439,409),SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1 (described inEuropean Patent No. 0293032), ITQ-1 (described in U.S. Pat. No.6,077,498), ITQ-2 (described in International Patent Publication No.WO97/17290), ITQ-30 (described in International Patent Publication No.WO2005118476), MCM-36 (described in U.S. Pat. No. 5,250,277), MCM-49(described in U.S. Pat. No. 5,236,575), MCM-56 (described in U.S. Pat.No. 5,362,697), and UZM-8 (described in U.S. Pat. No. 6,756,030). Theentire contents of the patents are incorporated herein by reference.

It is to be appreciated the MCM-22 family molecular sieves describedabove are distinguished from conventional large pore zeolite alkylationcatalysts, such as mordenite, in that the MCM-22 family materials have12-ring surface pockets which do not communicate with the 10-ringinternal pore system of the molecular sieve.

The zeolitic materials designated by the IZA-SC as being of the MWWtopology are multi-layered materials which have two pore systems arisingfrom the presence of both 10 and 12 membered rings. The Atlas of ZeoliteFramework Types classes five differently named materials as having thissame topology: MCM-22, ERB-1, ITQ-1, PSH-3, and SSZ-25.

The MCM-22 family molecular sieves have been found to be useful in avariety of hydrocarbon conversion processes. Examples of MCM-22 familymolecular sieve are MCM-22, MCM-49, MCM-56, ITQ-1, PSH-3, SSZ-25, andERB-1. Such molecular sieves are useful for alkylation of aromaticcompounds. For example, U.S. Pat. No. 6,936,744 discloses a process forproducing a monoalkylated aromatic compound, particularly cumene,comprising the step of contacting a polyalkylated aromatic compound withan alkylatable aromatic compound under at least partial liquid phaseconditions and in the presence of a transalkylation catalyst to producethe monoalkylated aromatic compound, wherein the transalkylationcatalyst comprises a mixture of at least two different crystallinemolecular sieves, wherein each of the molecular sieves is selected fromzeolite beta, zeolite Y, mordenite and a material having an X-raydiffraction pattern including d-spacing maxima at 12.4±0.25, 6.9±0.15,3.57±0.07 and 3.42±0.07 Angstroms.

The present disclosure relates to an improved process mechanism forproduction of monoalkylated aromatic compounds, particularlyethylbenzene, cumene or sec-butylbenzene, by the liquid or partialliquid phase alkylation of an alkylatable aromatic compound,particularly benzene. More particularly, the present process uses acatalyst composition comprising a porous crystalline material, thecatalyst manufactured from extrudate to comprise catalytic particulatematerial of from about 125 microns to about 790 microns in size andhaving an Effectiveness Factor, hereafter defined, increased from about25% to about 750% from that of the original extrudate, more specificallyfrom about 260 microns to about 700 microns in size with anEffectiveness Factor, hereafter defined, increased from about 50% toabout 650% from that of the original extrudate. The catalyst compositionfor use in the present disclosure will comprise catalytic particulatematerial having an external surface area to volume ratio of greater thanabout 79 cm⁻¹, more specifically from greater than about 79 cm⁻¹ toabout 374 cm⁻¹.

Effectiveness Factor is commonly defined as the rate of reaction in thepresence of mass transport limitations divided by the rate of reactionwithout mass transport limitation. A detailed discussion ofEffectiveness Factor can be found in general treatises on this subject,such as “Mass Transfer in Heterogeneous Catalysis” by C. N. Satterfield;and “Mass Transfer in Heterogeneous Catalysis”, Robert KriegerPublishing Co., Malabar, Fla., 1980, original edition, M.I.T. Press,Cambridge, Mass., 1970, incorporated herein by reference. In somecircumstances when the catalyst deactivates during the measurement, thereaction rate constant is measured excluding the effect of catalystdeactivation, such as the reaction rate constant measured byextrapolating the reaction rate prior to deactivation. In the presentdisclosure, effectiveness factor is calculated as the rate constant ofthe alkylation reaction of the catalyst being tested divided by the rateconstant of the alkylation reaction without mass transfer limitation.The calculation of the rate constant of the alkylation reaction is basedupon a solution for the second order rate expression in a batch reactorwhich can also be found in “Elements of Chemical Reaction Engineering”,Fogler, H. Scott, P T R Prentice-Hall, Inc., 1992, §8.3.1 & §5.6.2.Further details for batch cumene testing can be found in the subsequentsection “Test Sequence for Cumene Manufacture in a Batch Test.” Thesecond order rate constant measured at conditions without mass transferlimitation is calculated by estimating from the measured rates what themaximum rate of reaction would be with an infinitely small particle,wherein the rate constant is measured at conditions withoutdeactivation, such as by extrapolating the reaction rate prior todeactivation

The term “aromatic” in reference to the alkylatable aromatic compoundswhich may be useful as feedstock herein is to be understood inaccordance with its art-recognized scope. This includes alkylsubstituted and unsubstituted mono- and polynuclear compounds. Compoundsof an aromatic character that possess a heteroatom may also be usefulprovided sufficient catalytic activity is maintained under the reactionconditions selected.

Substituted aromatic compounds that can be alkylated herein must possessat least one hydrogen atom directly bonded to the aromatic nucleus. Thearomatic rings can be substituted with one or more alkyl, aryl, alkaryl,alkoxy, aryloxy, cycloalkyl, halide, and/or other groups that do notinterfere with the alkylation reaction.

Suitable aromatic compounds include benzene, naphthalene, anthracene,naphthacene, perylene, coronene, and phenanthrene, with benzene beingpreferred.

Generally the alkyl groups that can be present as substituents on thearomatic compound contain from 1 to about 22 carbon atoms and usuallyfrom about 1 to 8 carbon atoms, and most usually from about 1 to 4carbon atoms.

Suitable alkyl substituted aromatic compounds include toluene, xylene,isopropylbenzene, n-propylbenzene, alpha-methylnaphthalene,ethylbenzene, mesitylene, durene, cymenes, butylbenzene, pseudocumene,o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, isoamylbenzene,isohexylbenzene, pentaethylbenzene, pentamethylbenzene;1,2,3,4-tetraethylbenzene; 1,2,3,5-tetramethylbenzene;1,2,4-triethylbenzene; 1,2,3-trimethylbenzene, m-butyltoluene;p-butyltoluene; 3,5-diethyltoluene; o-ethyltoluene; p-ethyltoluene;m-propyltoluene; 4-ethyl-m-xylene; dimethylnaphthalenes;ethylnaphthalene; 2,3-dimethylanthracene; 9-ethylanthracene;2-methylanthracene; o-methylanthracene; 9,10-dimethylphenanthrene; and3-methyl-phenanthrene. Higher molecular weight alkylaromatic compoundscan also be used as starting materials and include aromatic organicssuch as are produced by the alkylation of aromatic organics with olefinoligomers. Such products are frequently referred to in the art asalkylate and include hexylbenzene, nonylbenzene, dodecylbenzene,pentadecylbenzene, hexyltoluene, nonyltoluene, dodecyltoluene,pentadecytoluene, etc. Very often alkylate is obtained as a high boilingfraction in which the alkyl group attached to the aromatic nucleusvaries in size from about C₆ to about C₁₂. When cumene or ethylbenzeneis the desired product, the present process produces acceptably littleby-products such as n-propyl benzene and xylenes respectively. Theseby-products made in such instances may be less than about 100 wppm.

Reformate containing a mixture of benzene, toluene and/or xyleneconstitutes a particularly useful feed for the alkylation process ofthis disclosure.

The alkylating agents that may be useful in the process of thisdisclosure generally include any aliphatic or aromatic organic compoundhaving one or more available alkylating aliphatic groups capable ofreaction with the alkylatable aromatic compound, preferably with thealkylating group possessing from 1 to 5 carbon atoms. Examples ofsuitable alkylating agents are olefins such as ethylene, propylene, thebutenes such as, for example, 1-butene, 2-butene or isobutylene, and thepentenes; alcohols (inclusive of monoalcohols, dialcohols, trialcohols,etc.) such as methanol, ethanol, the propanols, the butanols, and thepentanols; aldehydes such as formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, and n-valeraldehyde; and alkyl halidessuch as methyl chloride, ethyl chloride, the propyl chlorides, the butylchlorides, and the pentyl chlorides, and so forth. Mixtures of thesecompounds may also be useful, such as, for example, propylene andpropanol mixtures.

Mixtures of light olefins are useful as alkylating agents in thealkylation process of this disclosure. Accordingly, mixtures ofethylene, propylene, butenes, and/or pentenes which are majorconstituents of a variety of refinery streams, e.g., fuel gas, gas plantoff-gas containing ethylene, propylene, etc., naphtha cracker off-gascontaining light olefins, refinery FCC propane/propylene streams, etc.,are useful alkylating agents. For example, a typical FCC light olefinstream possesses the following composition:

Wt. % Mole % Ethane 3.3 5.1 Ethylene 0.7 1.2 Propane 4.5 15.3 Propylene42.5 46.8 Isobutane 12.9 10.3 n-Butane 3.3 2.6 Butenes 22.1 18.32Pentanes 0.7 0.4

Reaction products that may be obtained from the process of the presentdisclosure include ethylbenzene from the reaction of benzene withethylene, cumene from the reaction of benzene with propylene,ethyltoluene from the reaction of toluene with ethylene, cymenes fromthe reaction of toluene with propylene, and sec-butylbenzene from thereaction of benzene and n-butenes. Particularly preferred processmechanisms of the disclosure relate to the production of cumene by thealkylation of benzene with propylene and production of ethylbenzene bythe alkylation of benzene with ethylene.

The reactants can be partially or completely in the liquid phase and canbe neat, i.e. free from intentional admixture or dilution with othermaterial, or they can be brought into contact with the catalystcomposition with the aid of carrier gases or diluents such as, forexample, hydrogen, methane and/or nitrogen.

The alkylation process of this disclosure may be conducted such that theorganic reactants, i.e., the alkylatable aromatic compound and thealkylating agent, are brought into contact with the presently requiredcatalyst in a suitable reaction zone under effective alkylationconditions. Such conditions include a temperature of from about 0° C. toabout 500° C., preferably from about 10° C. to about 260° C., a pressureof from about 20 to about 25000 kPa-a, preferably from about 100 toabout 5500 kPa-a, a molar ratio of alkylatable aromatic compound toalkylating agent of from about 0.1:1 to about 50:1, preferably fromabout 0.5:1 to about 10:1, and a feed weight hourly space velocity(WHSV) based on the alkylating agent of from about 0.1 to 500 hr⁻¹,preferably from about 0.1 to about 100 hr⁻¹.

When benzene is alkylated with ethylene to produce ethylbenzene, thealkylation reaction is preferably carried out in the liquid phase underconditions including a temperature of from about 150° C. to about 300°C., more preferably from about 170° C. to about 260° C.; a pressure upto about 20400 kPa-a, more preferably from about 2000 kPa-a to about5500 kPa-a; a weight hourly space velocity (WHSV) based on the ethylenealkylating agent of from about 0.1 to about 20 hr⁻¹, more preferablyfrom about 0.5 to about 6 hr⁻¹; and a ratio of benzene to ethylene inthe alkylation reaction zone of from about 0.5:1 to about 100:1 molar,preferably 0.5:1 to 50:1 molar, more preferably from about 1:1 to about30:1 molar, most preferably from about 1:1 to about 10:1 molar.

When benzene is alkylated with propylene to produce cumene, the reactionmay also take place under liquid phase conditions including atemperature of up to about 250° C., preferably up to about 150° C.,e.g., from about 10° C. to about 125° C.; a pressure of about 25000kPa-a or less, e.g., from about 100 to about 3000 kPa-a; a weight hourlyspace velocity (WHSV) based on propylene alkylating agent of from about0.1 hr⁻¹ to about 250 hr⁻¹, preferably from about 1 hr⁻¹ to about 50hr⁻¹; and a ratio of benzene to propylene in the alkylation reactionzone of from about 0.5:1 to about 100:1 molar, preferably 0.5:1 to 50:1molar, more preferably from about 1:1 to about 30:1 molar, mostpreferably from about 1:1 to about 10:1 molar.

When benzene is alkylated with a butene to produce sec-butylbenzene, thereaction may also take place under liquid phase conditions including atemperature of up to about 250° C., preferably up to about 150° C.,e.g., from about 10° C. to about 125° C.; a pressure of about 25000kPa-a or less, e.g., from about 1 to about 3000 kPa-a; a weight hourlyspace velocity (WHSV) based on the butene alkylating agent of from about0.1 hr⁻¹ to about 250 hr⁻¹, preferably from about 1 hr⁻¹ to about 50hr⁻¹; and a ratio of benzene to butene in the alkylation reaction zoneof from about 0.5:1 to about 100:1 molar, preferably 0.5:1 to 50:1molar, more preferably from about 1:1 to about 30:1 molar, mostpreferably from about 1:1 to about 10:1 molar.

The reaction zone useful for the present disclosure due to the smallparticulate size of the catalyst may be, for example, in a fixed bedoperation with low linear velocity so as not to create unacceptablepressure drop; in a continuous stirred tank reactor (CSTR); in anebullating bed operating in up-flow mode such that the catalyst moves inan ebullating fashion; or in a slurry loop in which the catalyst andfeedstock form a loose slurry pumped through a pipe serving as thereactor.

A fixed bed operation useful in the present disclosure with low linearvelocity so as not to create unacceptable pressure drop is depicted in“Elements of Chemical Reaction Engineering”, Fogler, H. Scott, P T RPrentice-Hall, Inc., 1992, §4.4 & §8.3.2, and “Perry's ChemicalEngineers' Handbook”, 7th ed., Perry, Robert H. and Green, Don W.,McGraw-Hill Companies, Inc., 1997, §23, incorporated herein byreference.

A continuous stirred tank reactor (CSTR) useful in the presentdisclosure is depicted in “Elements of Chemical Reaction Engineering”,Fogler, H. Scott, P T R Prentice-Hall, Inc., 1992, §8.3.1 & §5.6.2, and“Perry's Chemical Engineers' Handbook”, 7th ed., Perry, Robert H. andGreen, Don W., McGraw-Hill Companies, Inc., 1997, §23, incorporatedherein by reference.

An ebullating bed useful in the present disclosure operating in up-flowmode such that the catalyst moves in an ebullating fashion is depictedin “Perry's Chemical Engineers' Handbook”, 7th ed., Perry, Robert H. andGreen, Don W., McGraw-Hill Companies, Inc., 1997, §23, incorporatedherein by reference.

A slurry reactor in which the catalyst and feedstock form loose slurrystirred in a tank or pumped through a pipe serving as the reactor usefulin the present disclosure is depicted in “Chemical and CatalyticReaction Engineering:, Carberry, James J., McGraw-Hill, Inc., 1976,§10.6 and “Perry's Chemical Engineers' Handbook”, 7th ed., Perry, RobertH. and Green, Don W., McGraw-Hill Companies, Inc., 1997, §23,incorporated herein by reference.

The catalyst for use in the present disclosure may comprise acrystalline molecular sieve having the structure of zeolite Beta(described in U.S. Pat. No. 3,308,069) or an MWW structure type such as,for example, those having an X-ray diffraction pattern includingd-spacing maxima at 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07Angstroms. Examples of MWW structure type materials include MCM-22(described in U.S. Pat. No. 4,954,325), PSH-3 (described in U.S. Pat.No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667), ERB-1(described in European Patent No. 0293032), ITQ-1 (described in U.S.Pat. No. 6,077,498), ITQ-2 (described in U.S. Pat. No. 6,231,751),ITQ-30 (described in WO 2005-118476), MCM-36 (described in U.S. Pat. No.5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575) and MCM-56(described in U.S. Pat. No. 5,362,697). The catalyst can include themolecular sieve in unbound or self-bound form or, alternatively, themolecular sieve can be combined in a conventional manner with an oxidebinder as hereinafter detailed. For the improvement of the presentdisclosure, the average particle size of the catalyst manufactured fromextrudate must be from about 125 microns to about 790 microns in sizeand have an Effectiveness Factor increased from about 25% to about 750%from that of the original extrudate. More specifically, the catalystmanufactured from extrudate will be from about 260 microns to about 700microns in size with an Effectiveness Factor increased by from about 50%to about 650%. Also, the external surface area to volume ratio of thecatalyst will be greater than about 79 cm⁻¹, preferably from greaterthan about 79 cm⁻¹ to about 374 cm⁻¹.

For the reaction process of the present disclosure, the alkylationreactor effluent contains excess aromatic feed, monoalkylated product,polyalkylated products, and various impurities. The aromatic feed isrecovered by distillation and recycled to the alkylation reactor.Usually a small bleed is taken from the recycle stream to eliminateunreactive impurities from the loop. The bottoms from the distillationmay be further distilled to separate monoalkylated product frompolyalkylated products and other heavies.

Any polyalkylated products separated from the alkylation reactoreffluent may be reacted with additional aromatic feed in atransalkylation reactor, separate from the alkylation reactor, over asuitable transalkylation catalyst. The transalkylation catalyst maycomprise one or a mixture of crystalline molecular sieves having thestructure of zeolite Beta, zeolite Y, mordenite or a MCM-22 familymaterial having an X-ray diffraction pattern including d-spacing maximaat 12.4±0.25, 6.9±0.15, 3.57±0.07 and 3.42±0.07 Angstroms.

The X-ray diffraction data used to characterize the above catalyststructures are obtained by standard techniques using the K-alpha doubletof copper as the incident radiation and a diffractometer equipped with ascintillation counter and associated computer as the collection system.Materials having the above X-ray diffraction lines include, for example,MCM-22 (described in U.S. Pat. No. 4,954,325), PSH-3 (described in U.S.Pat. No. 4,439,409), SSZ-25 (described in U.S. Pat. No. 4,826,667),ERB-1 (described in European Patent No. 0293032), ITQ-1 (described inU.S. Pat. No. 6,077,498), ITQ-2 (described in U.S. Pat. No. 6,231,751),ITQ-30 (described in WO 2005-118476), MCM-36 (described in U.S. Pat. No.5,250,277), MCM-49 (described in U.S. Pat. No. 5,236,575) and MCM-56(described in U.S. Pat. No. 5,362,697), with MCM-22 being particularlypreferred.

Zeolite Beta is disclosed in U.S. Pat. No. 3,308,069. Zeolite Y andmordenite occur naturally but may also be used in one of their syntheticforms, such as Ultrastable Y (USY), which is disclosed in U.S. Pat. No.3,449,070, Rare earth exchanged Y (REY), which is disclosed in U.S. Pat.No. 4,415,438, and TEA-mordenite (i.e., synthetic mordenite preparedfrom a reaction mixture comprising a tetraethylammonium directing agent,“R”), which is disclosed in U.S. Pat. Nos. 3,766,093 and 3,894,104.However, in the case of TEA-mordenite for use in the transalkylationcatalyst, the particular synthesis regimes described in the patentsnoted lead to the production of a mordenite product composed ofpredominantly large crystals with a size greater than 1 micron andtypically around 5 to 10 micron. It has been found that controlling thesynthesis so that the resultant TEA-mordenite has an average crystalsize of less than 0.5 micron results in a transalkylation catalyst withmaterially enhanced activity for liquid phase aromatics transalkylation.

The small crystal TEA-mordenite desired for transalkylation can beproduced by crystallization from a synthesis mixture having a molarcomposition within the following ranges:

$\begin{matrix}\; & \; & \underset{\_}{Useful} & \underset{\_}{Preferred} \\{{R/R} + {Na} +} & = & {> 0.4} & {0.45 - 0.7} \\{{OH} - {{/{SiO}}\; 2}} & = & {< 0.22} & {0.05 - 0.2} \\{{{Si}/{Al}}\; 2} & = & {> {30 - 90}} & {35 - 50} \\{H_{2}{O/{OH}}} & = & {50 - 70} & {50 - 60}\end{matrix}$

The crystallization from this synthesis mixture is conducted at atemperature of 90 to 200° C., for a time of 6 to 180 hours.

The catalyst for use in the present disclosure may include an inorganicoxide material matrix or binder. Such matrix materials include syntheticor naturally occurring substances as well as inorganic materials such asclay, silica and/or metal oxides. The latter may be either naturallyoccurring or in the form of gelatinous precipitates or gels includingmixtures of silica and metal oxides. Naturally occurring clays which canbe composited with the inorganic oxide material include those of themontmorillonite and kaolin families, which families include thesubbentonites and the kaolins commonly known as Dixie, McNamee, Georgiaand Florida clays or others in which the main mineral constituent ishalloysite, kaolinite, dickite, nacrite or anauxite. Such clays can beused in the raw state as originally mined or initially subjected tocalcination, acid treatment or chemical modification.

Specific useful catalyst matrix or binder materials employed hereininclude silica, alumina, zirconia, titania, silica-alumina,silica-magnesia, silica-zirconia, silica-thoria, silica-beryllia,silica-titania as well as ternary compositions such assilica-alumina-thoria, silica-alumina-zirconia, silica-alumina-magnesiaand silica-magnesia-zirconia. The matrix can be in the form of a cogel.A mixture of these components could also be used.

The relative proportions of crystalline molecular sieve and binder ormatrix, if present, may vary widely with the crystalline molecular sievecontent ranging from about 1 to about 99 percent by weight, and moreusually in the range of about 30 to about 80 percent by weight of thetotal catalyst. Of course, the catalyst may comprise a self-boundmolecular sieve or an unbound molecular sieve, thereby being about 100%crystalline molecular sieve.

The catalyst for use in the present disclosure, or its crystallinemolecular sieve component, may or may not contain addedfunctionalization, such as, for example, a metal of Group 6 (e.g. Cr andMo), Group 7 (e.g. Mn and Re) or Groups 8, 9, and 10 (e.g. Co, Ni, Pdand Pt), or phosphorus.

The catalyst for use in the present disclosure must be manufactured formextrudate and have an average particle size within the narrow range offrom about 125 to about 790 microns and have an Effectiveness Factorincreased from about 25% to about 750% from that of the originalextrudate, for example, from about 260 to about 700 microns in size withan Effectiveness Factor increased from about 50% to about 650% from thatof the original extrudate. It may be made, for example, by reducing theparticle size of 0.159 cm cylindrical extrudates or 0.127 cm shaped,e.g. trilobal or quadrulobal, extrudates by crushing and sieving. Asummary of the molecular sieves and/or zeolites, in terms of production,modification and characterization of molecular sieves, is described inthe book “Molecular Sieves—Principles of Synthesis and Identification”;(R. Szostak, Blackie Academic & Professional, London, 1998, SecondEdition). In addition to molecular sieves, amorphous materials, chieflysilica, aluminum silicate and aluminum oxide, have been used asadsorbents and catalyst supports. A number of long-known techniques,like spray drying, prilling, pelletizing and extrusion, have been andare being used to produce macrostructures in the form of, for example,spherical particles, extrudates, pellets and tablets of both microporousand other types of porous materials for use in catalysis, adsorption andion exchange. A summary of these techniques is described in “CatalystManufacture,” A. B. Stiles and T. A. Koch, Marcel Dekker, New York,1995.

Non-limiting examples of the present disclosure involving an alkylationmechanism are described with reference to the following experiments. Inthe experiments, catalyst activity is defined by reference to thekinetic rate constant which is determined by assuming second orderreaction kinetics. For a discussion of the determination of the kineticrate constant, reference is directed to “Heterogeneous Reactions:Analysis, Examples, and Reactor Design, Vol. 2: Fluid-Fluid-SolidReactions” by L. K. Doraiswamy and M. M. Sharma, John Wiley & Sons, NewYork (1994) and to “Chemical Reaction Engineering” by 0. Levenspiel,Wiley Eastern Limited, New Delhi (1972).

Catalysts for Testing

In these experiments, catalyst materials tested are listed below:

“Material 1” was MCM-49 catalyst that was prepared by extruding amixture of 80 wt. % MCM-49 crystals and 20 wt. % alumina into solidquadrulobal extrudates having a diameter of 0.127 cm and a length of0.635 cm (hereinafter “MCM-49 quadrulobal catalyst”). The resultantcatalyst particles had a surface area to volume ratio of 78 cm⁻¹ and anEffectiveness Factor of 0.18.

“Material 2” was prepared from Material 1 by crushing and sieving the0.127 cm MCM-49 quadrulobal catalyst to a range of particle sizes from250 to 297 microns. The resultant catalyst particles had a surface areato volume ratio of 344 cm⁻¹ and an Effectiveness Factor of 0.65. Theincrease in Effectiveness Factor from the Material 1 catalyst was 261%.

“Material 3” was MCM-22 catalyst that was prepared by extruding amixture of 65 wt. % MCM-22 crystals and 35 wt. % alumina into solidcylindrical extrudates having a diameter of 0.159 cm and a length of0.635 cm (hereinafter “MCM-22 cylindrical catalyst”). The resultantMCM-22 cylindrical catalyst particles had a surface area to volume ratioof 34.6 cm⁻¹ and an Effectiveness Factor of 0.08.

“Material 4” was prepared from Material 3 by crushing and sieving the0.159 cm MCM-22 cylindrical catalyst to a range of particle sizes from250 to 297 microns. The resultant catalyst particles had a surface areato volume ratio of 344 cm⁻¹ and an Effectiveness Factor of 0.55. Theincrease in Effectiveness Factor from the Material 3 catalyst was 587%.

“Material 5” was zeolite Beta catalyst that was prepared by extruding amixture of 80 wt. % zeolite Beta crystals and 20 wt. % alumina intosolid quadrulobal extrudates having a diameter of 0.127 cm ( 1/20 inch)and a length of 0.635 cm (hereinafter “Beta quadrulobal catalyst”). Theresultant Beta quadrulobal catalyst particles had a surface area tovolume ratio of 78 cm⁻¹ and an Effectiveness Factor of 0.21 based on thesecond order rate constant measured by extrapolating the reaction rateprior to deactivation and without mass transport limitations.

“Material 6” was prepared from Material 5 by crushing and sieving the0.127 cm Beta quadrulobal catalyst to a range of particle sizes from 250to 297 microns. The resultant catalyst particles had a surface area tovolume ratio of 344 cm⁻¹ and an Effectiveness Factor of 0.73 based onthe second order rate constant measured by extrapolating the reactionrate prior to deactivation and without mass transport limitations. Theincrease in Effectiveness Factor from the Material 5 catalyst is 347%.

Catalyst Reactivity Measurement Procedure

Equipment for Batch Tests

A 300 ml Parr batch reaction vessel for cumene manufacture and a 600 mlParr batch reaction vessel for ethylbenzene manufacture were eachequipped with a stir rod and static catalyst basket was used for theactivity and selectivity measurements. The reaction vessels were fittedwith two removable vessels for the introduction of benzene and propyleneor ethylbenzene respectively.

Feed Pretreatment

Benzene

Benzene was obtained from a commercial source. The benzene was passedthrough a pretreatment vessel (2 L Hoke vessel) containing equal parts(by volume) molecular sieve 13×, molecular sieve 4A, Engelhard F-24Clay, and Selexsorb CD (in order from inlet to outlet), and then througha 250 ml vessel containing MCM-22 catalyst. All feed pretreatmentmaterials were dried in a 260° C. oven for 12 hours before using.

Propylene and Ethylene

Propylene and ethylene were obtained from a commercial specialty gasessource and were polymer grade. The propylene and ethylene were passedthrough a 300 ml vessel containing pretreatment materials in thefollowing order:

a. 150 ml molecular sieve 5A

b. 150 ml Selexsorb CD

Both guard-bed materials were dried in a 260° C. oven for 12 hoursbefore using.

Nitrogen

Nitrogen was ultra high purity grade and obtained from a commercialspecialty gases source. The nitrogen was passed through a 300 ml vesselcontaining pretreatment materials in the following order:

a. 150 ml molecular sieve 5A

b. 150 ml Selexsorb CD

Both guard-bed materials were dried in a 260° C. oven for 12 hoursbefore using.

Catalyst Preparation and Loading

A 2 gram sample of catalyst was dried in an oven in air at 260° C. for 2hours. The catalyst was removed from the oven and immediately 1 gram ofcatalyst was weighed. Quartz chips were used to line the bottom of abasket followed by loading of the catalyst into the basket on top of thefirst layer of quartz. Quartz chips were then placed on top of thecatalyst. The basket containing the catalyst and quartz chips was placedin an oven at 260° C. overnight in air for about 16 hours.

The reactor and all lines were cleaned with a suitable solvent (such astoluene) before each experiment. The reactor and all lines were dried inair after cleaning to remove all traces of cleaning solvent. The basketcontaining the catalyst and quartz chips was removed from the oven andimmediately placed in the reactor and the reactor was immediatelyassembled.

Test Sequence for Cumene Manufacture in a Batch Test

The reactor temperature was set to 170° C. and purged with 100 sccm ofthe ultra high purity nitrogen for 2 hours. After nitrogen purged thereactor for 2 hours, the reactor temperature was reduced to 130° C., thenitrogen purge was discontinued and the reactor vent closed. A 156.1gram quantity of benzene was loaded into a 300 ml transfer vessel,performed in a closed system. The benzene vessel was pressurized to 790kPa-a with the ultra high purity nitrogen and the benzene wastransferred into the reactor. The agitator speed was set to 500 rpm andthe reactor was allowed to equilibrate for 1 hour.

A 75 ml Hoke transfer vessel was then filled with 28.1 grams of liquidpropylene and connected to the reactor vessel, and then connected with2169 kPa-a ultra high purity nitrogen. After the one-hour benzene stirtime had elapsed, the propylene was transferred from the Hoke vessel tothe reactor. The 2169 kPa-a nitrogen source was maintained connected tothe propylene vessel and open to the reactor during the entire run tomaintain constant reaction pressure during the test. Liquid productsamples were taken at 30, 60, 120, 150, 180 and 240 minutes afteraddition of the propylene.

Test Sequence for Ethylbenzene Manufacture in a Batch Test

The reactor temperature was set to 170° C. and purged with 100 sccm ofthe ultra high purity nitrogen for 2 hours. After nitrogen purged thereactor for 2 hours, the reactor temperature was reduced to 220° C., thenitrogen purge was discontinued and the reactor vent closed. A 195 gramquantity of benzene was loaded into a 600 ml transfer vessel, performedin a closed system. The benzene vessel was pressurized to 790 kPa-a withthe ultra high purity nitrogen and the benzene was transferred into thereactor. The agitator speed was set to 500 rpm and the reactor wasallowed to equilibrate for 1 hour. After the one-hour benzene stir timehad elapsed, 39.4 grams of ethylene was introduced into the reactor. A2169 kPa-a nitrogen source was maintained connected to the reactionvessel during the entire run to maintain constant reaction pressureduring the test. Liquid product samples were taken at 30, 60, 120, 150,180 and 240 minutes after addition of the ethylene.

Test Sequence for Cumene Manufacture in a Fixed Bed Test

These experiments were conducted in a fixed bed ⅜″ or ¾″ OD tubularreactor in a downflow configuration. The reactor furnace was controlledin isothermal mode. The catalyst was dried off-line at 260° C. in airfor 2 hours before loading into the reactor. Experiments were conductedwith catalyst as whole extrudates loaded into the ⅜″ reactor. Thecatalyst bed was axially centered in the middle furnace zone. Thecatalyst used was extrudate form, spray-dried form, or extrudate crushedand sized to 250 microns to 297 microns depending on the experiment. Allcatalysts were packed with inert sand to fill the interstitial voidspaces. Reaction conditions were 125° C., 2169 kPa-a and thebenzene/propylene molar ratio was 2.8/1. Weight hourly space velocitywas adjusted during the experiments and ranged from 1 hr⁻¹ to 320 hr⁻¹on a propylene basis.

At reactor start-up, the reactor was brought to reaction pressure of2169 kPa-a with the ultra high purity nitrogen, and heated to reactiontemperature of 125° C. prior to introducing the feed. The catalyst wasallowed to equilibrate for 1 to 2 days to achieve steady state beforedata was collected.

The MCM-49 quadrulobal catalyst (Material 1), the MCM-22 cylindricalcatalyst (Material 3), and the 250 to 297 micron catalysts (average of274 microns) prepared from them by crushing and sieving (Materials 2 and4, respectively) were tested according the cumene batch test procedure.The MCM-49 quadrulobal catalyst (Material 1) and the 250 to 297 microncatalyst (average of 274 microns) prepared from it by crushing andsieving (Material 2) were tested according the ethylbenzene batch testprocedure. The MCM-49 quadrulobal catalyst (Material 1), the Betacylindrical catalyst (Material 5), and the 250 to 297 micron catalysts(average of 274 microns) prepared from them by crushing and sieving(Materials 2 and 6, respectively) were tested according the cumene fixedbed procedure.

Example 1

In these experiments, cumene was manufactured by contacting 5.55 partsby weight benzene and 1 part by weight propylene in the batch slurryreactor using the procedure detailed above for Test Sequence for CumeneManufacture in a Batch Test over catalysts selected individually fromMaterials 1, 2 and 3. Cumene (isopropylbenzene, IPB) anddiisopropylbenzene (DIPB) products were collected from each experimentand it was found that catalyst for use in the present disclosure, i.e.Material 2, provided about 30% reduction in the DIPB/IPB ratio. Also,Material 2 yielded about 288% higher activity than Material 1, and about600% higher activity than Material 3.

Example 2

In these experiments, cumene was manufactured by contacting 5.55 partsby weight benzene and 1 part by weight propylene in the batch slurryreactor using the procedure detailed above for Test Sequence for CumeneManufacture in a Batch Test over catalyst comprising the 0.127 cm MCM-49quadrulobal catalyst (Material 1) and the 250 to 297 micron catalystprepared from it by crushing and sieving (Material 2). Cumene(isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products werecollected from each experiment and it was found that Material 2 againprovided a 30% reduction in the DIPB/IPB ratio.

Example 3

In these experiments, cumene was manufactured by contacting 5.55 partsby weight benzene and 1 part by weight propylene in the batch slurryreactor using the procedure detailed above for Test Sequence for CumeneManufacture in a Batch Test over catalyst comprising the MCM-22cylindrical catalyst (Material 3) and the 250 to 297 micron catalystprepared from it by crushing and sieving (Material 4). Cumene(isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products werecollected from each experiment and it was found that catalyst Material 4provided a 13% reduction in the DIPB/IPB ratio.

Example 4

In these experiments, ethylbenzene was manufactured by contacting 0.95parts by weight benzene and 1 part by weight ethylene in the batchslurry reactor using the procedure detailed above for Test Sequence forEthylbenzene Manufacture in a Batch Test over catalyst comprising the0.127 cm MCM-49 quadrulobal catalyst (Material 1) and the 250 to 297micron catalyst prepared from it by crushing and sieving (Material 2).Ethylbenzene (EB) and diethylbenzene (DEB) products were collected fromeach experiment and it was found that catalyst Material 2 provided a 23%reduction in the DEB/EB ratio.

Example 5

In these experiments, cumene was manufactured by contacting 5.2 parts byweight benzene and 1 part by weight propylene in the fixed bed microreactor using the procedure detailed above for Test Sequence for CumeneManufacture in a Fixed Bed Test over catalyst comprising the 0.127 cmMCM-49 quadrulobal catalyst (Material 1) and the 250 to 297 microncatalyst prepared from it by crushing and sieving (Material 2). Cumene(isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products werecollected from each experiment and it was found that Example 8 provideda 54% reduction in the DIPB/IPB ratio.

Example 6

In these experiments, cumene was manufactured by contacting 5.2 parts byweight benzene and 1 part by weight propylene in the batch slurryreactor using the procedure detailed above for Test Sequence for CumeneManufacture in a Batch Test over catalyst comprising the Betaquadrulobal catalyst (Material 5) and the 250 to 297 micron catalystprepared from it by crushing and sieving (Material 6). Cumene(isopropylbenzene, IPB) and diisopropylbenzene (DIPB) products werecollected from each experiment and it was found that catalyst Material 6provided a 65% reduction in the DIPB/IPB ratio before deactivation.

Example 7

In a simulated CSTR reaction conducted in the liquid phase at 130° C.,2413 kPa-a inlet pressure and WHSV of 76.5 hr^(˜)1 based on propylene,the catalyst volume of 16.8 m³ comprising catalyst Material 1, feedstockcomprising 25 parts by weight propylene and 75 parts by weight benzene,propylene conversion was 32.4%. By simulating the same CSTR reactionwith catalyst comprising the MCM-49 quadrulobal catalyst having beencrushed and sieved to be 250 to 297 microns in size (Material 2),propylene conversion was found to be 66.2%. This example shows that in acontinuous stirred tank reactor, catalyst particles sized to be withinthe requirements of the present disclosure are effective in increasingconversion of propylene in reaction with benzene in the liquid phase.

All patents, patent applications, test procedures, articles,publications, and other documents cited herein are fully incorporated byreference to the extent such disclosure is not inconsistent with thisdisclosure and for all jurisdictions in which such incorporation ispermitted.

When numerical lower limits and numerical upper limits are listedherein, ranges from any lower limit to any upper limit are contemplated.

While the illustrative embodiments of the disclosure have been describedwith particularity, it will be understood that various othermodifications will be apparent to and can be readily made by thoseskilled in the art without departing from the spirit and scope of thedisclosure. Accordingly, it is not intended that the scope of the claimsappended hereto be limited to the examples and descriptions set forthherein but rather that the claims be construed as encompassing all thefeatures of patentable novelty which reside in the present disclosure,including all features which would be treated as equivalents thereof bythose skilled in the art to which the disclosure pertains.

1. In a process for manufacturing a monoalkylated aromatic compound in areaction zone, said process comprising contacting a feedstock comprisingan alkylatable aromatic compound and an alkylating agent with acatalytic particulate material at alkylation reaction conditions, theimprovement wherein said catalytic particulate material is manufacturedfrom extrudate and comprises particles of from about 125 microns toabout 790 microns in size having an Effectiveness Factor increased fromabout 25% to about 750% from that of the original extrudate, and has anexternal surface area to volume ratio of greater than about 79 cm⁻¹,wherein the catalytic particulate material comprises porous crystallinematerial is MCM-56, wherein said alkylating agent is ethylene, saidalkylatable aromatic compound is benzene and said monoalkylated aromaticcompound is ethylbenzene, or wherein said alkylating agent is propylene,said alkylatable aromatic compound is benzene and said monoalkylatedaromatic compound is cumene.
 2. The process of claim 1, wherein saidcatalytic particulate material comprises particles of from about 260microns to about 700 microns in size having an Effectiveness Factorincreased from about 50% to about 650% from that of the originalextrudate and has an external surface area to volume ratio of fromgreater than about 79 cm⁻¹ to about 374 cm⁻¹.
 3. The process of claim 1,wherein said reaction conditions include a temperature of from about 0°C. to about 500° C., a pressure of from about 0.2 to about 25000 kPa-a,a molar ratio of alkylatable aromatic compound to alkylating agent offrom about 0.1:1 to about 50:1, and a feed weight hourly space velocity(WHSV) based on the alkylating agent of from about 0.1 to 500 hr⁻¹. 4.The process of claim 1, wherein said reaction zone is in at least one ofa fixed bed reactor, a continuous stirred tank reactor, and anebullating bed reactor operating in up-flow mode.
 5. The process ofclaim 1, wherein said reaction zone is in a slurry loop reactor in whichthe catalytic particulate material and feedstock form loose slurrypumped through a pipe.
 6. The process of claim 1, wherein said reactionconditions include a temperature of from about 150° C. to about 300° C.,a pressure up to about 20400 kPa-a, a weight hourly space velocity(WHSV) based on the ethylene alkylating agent of from about 0.1 hr⁻¹ toabout 20 hr⁻¹, and a ratio of benzene to ethylene in the reaction zoneof from about 0.5:1 to about 50:1 molar.
 7. The process of claim 1,wherein said reaction conditions include a temperature of up to about250° C., a pressure of about 25000 kPa-a or less, a weight hourly spacevelocity (WHSV) based on propylene alkylating agent of from about 0.1hr⁻¹ to about 250 hr⁻¹, and a ratio of benzene to propylene in thereaction zone of from about 0.5:1 to about 50:1 molar.